On the Role of Charge Transfer in Many‐Body Non‐Covalent Interactions

Charge transfer between molecules can be arbitrarily switched on and off using Constrained Density Functional Theory (cDFT). We use it to quantify the contribution of charge transfer to the three-body interaction energy in molecular trimers and its indirect effect on the interactions in the system.

Abstract

Charge transfer is one of the mechanisms involved in non-covalent interactions. In molecular dimers, its contribution to pairwise interaction energies has been studied extensively using a variety of interaction energy decomposition schemes. In polar interactions such as hydrogen bonds, it can contribute ten or several tens of percent of the interaction energy. Less is known about its importance in higher-order interactions in many-body systems, mainly because of the lack of methods applicable to this problem. In this work, we extend our method for the quantification of the charge-transfer energy based on constrained DFT to many-body cases and apply it to model trimers extracted from molecular crystals. Our calculations show that charge transfer can account for a large fraction of the total three-body interaction energy. This also has implications for DFT calculations of many-body interactions in general as it is known that many DFT functionals struggle to describe charge-transfer effects correctly.

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